CN1096301A - The stabilising method of the nature rubber latex of deproteinization - Google Patents
The stabilising method of the nature rubber latex of deproteinization Download PDFInfo
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- CN1096301A CN1096301A CN94106006.3A CN94106006A CN1096301A CN 1096301 A CN1096301 A CN 1096301A CN 94106006 A CN94106006 A CN 94106006A CN 1096301 A CN1096301 A CN 1096301A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
- C08C1/04—Purifying; Deproteinising
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
- C08C1/06—Preservation of rubber latex
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Abstract
A kind of method of nature rubber latex of stable deproteinization is disclosed, comprise and add a kind of stablizer, this stablizer is selected from: (a) anion surfactant, (b) amphoterics, (c) nonionogenic tenside, (d) nonionic or amphoteric oligopolymer superpolymer and (e) anionic oligomer or superpolymer.By adding stablizer, the mechanical stability of the nature rubber latex of deproteinization improves greatly.
Description
The present invention relates to the stabilising method of the nature rubber latex of deproteinization.
So far, natural rubber is widely used as Industrial products, for example doughnut, transmission belt and pressure sensitive adhesive and household supplies such as gloves.The production method of these natural rubber articles is generally: the rubber constituent of the rubber liquid of nature rubber latex is condensed obtains rubber, this rubber is called wrinkle TR thin rubber plate or the dried untreated rubber sheet of cigarette, and rubber is further processed through following step: plasticate, add additive, molding and sulfuration.
Have recently and report: the medical appliance of natural rubber system such as surgical glove, various catheter and pain relieving cover can cause the patient respiration difficulty or produce anaphylaxis, for example blood vessel edema, urticaria, collapse and cyanosis.And reported case: when the women of allergies used the rubber gloves of natural rubber system, they had produced symptoms such as hand pain, urticaria or ocular angiogenesis edema.
These symptoms may be owing to have in the natural rubber that protein causes.The U.S. food and the drug control council (FDA) have required the production of natural rubber goods will reduce protein content.Thereby need from natural rubber, remove deproteinize.
Natural rubber obtains from Para rubber tree, be emulsion form, this emulsion contains rubber constituent, water, protein, inorganic salt and other impurity, slowly ooze out on the trunk that latex is severed from rubber producting plant, the emulsion of oozing out is collected with cup, condenses after gathering in refinery to obtain rubber (the dried untreated rubber sheet of wrinkle TR thin rubber plate or cigarette) or with the centrifugal latex obtain purifying that concentrates.
Protein content in the natural rubber is typically expressed as: the nitrogen content of measuring through the Ji Yeda method (N%) multiply by 6.3.Protein in the rubber that the inventor finds to obtain from latex can be by polypeptide at 3280cm
-1The infrared absorption at place confirms.
The inventor is in advance with present 3280cm
-1The nature rubber latex of the deproteinization of the no infrared absorption in place can be by the acquisition of such method: with proteolytic enzyme and tensio-active agent while or handle nature rubber latex successively, after system leaves standstill for some time, by centrifugal recovery rubber constituent (seeing that Japanese patent application 208754-208758/92(is equivalent to European patent application EP-A-0584597)).
(as vigorous stirring and friction) is stable (noncondensing) to general nature rubber latex on the market to mechanical stimulating action.This stability of latex is measured (JIS K-6381) by mechanical stability.
Above-mentioned deproteinization latex has a shortcoming, and that is exactly that mechanical stability is significantly less than general emulsion on the market.And the reason that mechanical stability reduces greatly also do not make clear, it is generally acknowledged: general glue protein of milk is adsorbed by micelle, be under the condition of alkalescence adding ammonia, and the negative charge that protein belt is very strong, the emulsion that contains micelle like this is in very stable status.On the contrary, the emulsion of deproteinization does not contain such protein protection layer, thus unstable, be easy to when being subjected to mechanical effect condense.
In addition, be used for removing proteinic tensio-active agent almost removed comprehensively, stay in the emulsion of deproteinization seldom in centrifugal treating subsequently.
Thereby, the purpose of this invention is to provide the method for the nature rubber latex of stablizing deproteinization, this kind rubber has exempted that fears are entertained that draws worry hypersensitive.The mechanical stability of the nature rubber latex by this method deproteinization can be improved.
Another object of the present invention provides the method for using aforesaid method to stablize the nature rubber latex of deproteinization.
The extensive investigations result of study shows that the inventor has been found that the mechanical stability of the nature rubber latex of the deproteinization that obtains with proteolytic enzyme and tensio-active agent processing can be greatly improved by adding specific tensio-active agent, oligopolymer or superpolymer.Finish the present invention based on this discovery.
The present invention relates to use a kind of stablizer that is selected from the compound of following one group of material as the nature rubber latex of deproteinization.
(a) anion surfactant,
(b) amphoteric tensio-active agent,
(c) nonionogenic tenside,
(d) nonionic or two oligomers or superpolymer and
(e) anionic oligomer or superpolymer.
The invention still further relates to the method for the nature rubber latex of stablizing deproteinization, comprise in the nature rubber latex of deproteinization, adding a kind of following one group of material stablizer that is selected from:
(a) anion surfactant,
(b) amphoteric tensio-active agent,
(c) nonionogenic tenside,
(d) nonionic or amphoteric oligopolymer or superpolymer and
(e) anionic oligomer or superpolymer.
Consumption is a 0.01-10%(weight), based on the total weight of latex.
Anion surfactant with used as stabilizers (a) comprises: carboxylic acid surfactant, sulfonic acid tensio-active agent, sulfuric acid ester surfactant and phosphate ester surfactants.
The example of carboxylic acid surfactant comprises: contain the soap of 6-30 carbon atom, and polycarboxylate, rosinate, dimerization hydrochlorate and floating oil fatty acid salt, the carboxylate salt that wherein contains 10-30 carbon atom are preferred.Containing those compounds that are less than 6 carbon atoms can not make mechanical stability obtain enough raisings.Those compounds that contain more than 30 carbon atoms are difficult to disperse in water.The example of preferred polycarboxylic acid comprises: straight chain or aromatics, saturated and undersaturated binary and tribasic carboxylic acid, they can be replaced by hydroxyl, amino, ketone group, for example: citric acid, keto-glutaric acid, Succinic Acid, fumaric acid, toxilic acid, oxysuccinic acid, L-glutamic acid, aspartic acid, phthalic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4, the 5-pyromellitic acid.
The example of sulfonic acid tensio-active agent comprises: alkylbenzene sulfonate, alkylsulfonate, sulfonated alkyl naphathalene, naphthalenesulfonate, diphenyl ether sulfonate, alpha-olefins sulfonate, dialkyl sulfosuccinate succinate, α-alpha-sulfonated fatty hydrochlorate, methyl oil base (oleyl) taurine.Wherein the moieties of alkylbenzene sulfonate, sulfonated alkyl naphathalene and dialkyl sulfosuccinate succinate contains 6-30 carbon atom, preferably 8-20 carbon atom.
The example of sulfuric acid ester surfactant comprises: alkyl sulfuric ester salt, polyoxyalkylene alkyl sulfuric ester salt, polyoxyalkylene alkyl phenyl ether sulfuric acid, polyoxyalkylene triphenylethylene phenol sulfuric acid salt and polyoxyalkylene toluylene phenol sulfuric acid salt.Wherein alkyl sulfuric ester salt, polyoxyalkylene alkyl sulfuric ester salt, polyoxyalkylene alkyl phenyl ether sulfuric acid and polyoxyalkylene toluylene phenol sulfuric acid salt.The example of polyoxyalkylenes comprises that those contain 1-100 mole, the group of 1-50 mole alkylene oxide hydrocarbon preferably, and described olefin oxide contains 2-4 carbon atom, preferably 2-3 carbon atom.The example of alkyl comprises that those contain 6-30 carbon atom, preferably contain the alkyl of 8-20 carbon atom.
The example of phosphate ester surfactants comprises: alkyl phosphate salt and polyoxyalkylene phosphate ester salt.Wherein preferred example comprises that alkyl phosphate salt and the polyoxyalkylene that moieties contains 8-20 carbon atom partly contains the 1-100 mole, preferably the 1-50 mole contains the polyoxyalkylene phosphate ester salt of the olefin oxide of 2-3 carbon atom.
Salt as these compounds of stablizer (a) comprises metal (for example Na, K, Ca, Mg or Zn) salt, ammonia salt and amine salt (for example triethanolamine salt).
Amphoterics as stablizer (b) comprises amino acid surfactant, betaine surfactants and amine oxide surfactant.
The preferred embodiment of amino acid surfactant comprises: an alkylamino alkylene carboxylate salt and dialkyl amido alkylen carboxylic acids salt.
The preferred embodiment of betaine (betaine) tensio-active agent comprises: alkyl dimethyl carboxyl ammonium methyl betaine, trialkyl sulfo group (sulfo) alkylidene group ammonium betaine, dialkyl group two polyoxyalkylenes ammonium sulfuric ester betaines, alkyl carboxyl methyl hydroxyethyl tetrahydroglyoxaline betaine.More preferably alkyl dimethyl carboxyl ammonium methyl betaine wherein.
The preferred embodiment of amine oxide surfactant comprises: alkyl dimethyl amine oxide.
In above-mentioned amphoterics, the example of alkyl comprise contain 6-30 carbon atom, preferably contain 8-20 carbon atom, more preferably contain the alkyl of 10-16 carbon atom.
Draw together polyoxyalkylene ether surface active agent, polyoxyalkylene ester surfactant, polyhydric alcohol fatty acid ester tensio-active agent, sugar fatty acid tensio-active agent and alkyl polyglucoside tensio-active agent as stablizer (c) ionic surfactant pack.
The example of polyoxyalkylene ether surface active agent comprises: polyoxyalkylene alkyl, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene polyol alkyl oxide, polyoxyalkylene styrenated phenol ether and polyoxyalkylene triphenylethylene phenol ether.The example of polyvalent alcohol comprises the polyvalent alcohol that contains 2-12 carbon atom in the polyoxyalkylene polyol alkyl oxide, for example propylene glycol, glycerine, sorbyl alcohol, sucrose, tetramethylolmethane and sorbitan.Wherein polyoxyalkylene alkyl and polyoxyalkylene alkyl phenyl ether are preferred.
The example of polyoxyalkylene ester surfactant comprises: the polyoxyalkylene fatty acid ester.
The example of polyhydric alcohol fatty acid ester tensio-active agent comprises: contain the fatty acid ester of polyvalent alcohol of 2-12 carbon atom and the fatty acid ester of polyoxyalkylene polyol.Example comprises Sorbitol Powder fatty acid ester, sorbitan fatty acid esters, lipid acid monoglyceryl ester, lipid acid two glyceryl ester and poly-glycerine fatty acid ester.The polyoxygenated alkene adduct of these ester cpds such as polyoxyalkylene sorbitan fatty acid esters and polyoxyalkylene glycerol fatty acid ester also can use.Wherein, the fatty acid ester of polyvalent alcohol is preferred.Example comprises more specifically: polyoxyalkylene Sorbitol Powder fatty acid ester, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene glycerol fatty acid ester and poly-glycerine fatty acid ester.
The example of sugar fatty acid ester surfactant comprises: the fatty acid ester of sucrose, glucose, maltose, fructose or saccharan.The adduct of the polyoxyalkylene of these esters also can use.Wherein, the fatty acid ester of sucrose is preferred.
The example of alkyl polyglucoside tensio-active agent comprises: alkyl glucoside and alkyl polyglucoside.The fatty acid ester of these compounds also can use.The polyoxygenated alkene adduct of these compounds also can use.Wherein the polyoxygenated alkene adduct of alkyl polyglucoside and alkyl glucoside is preferred.
In above-mentioned nonionogenic tenside, the example of alkyl comprises: the alkyl that contains 4-30 carbon atom.Polyalkylene oxide groups comprises that those alkylene moiety contain the group of 2-4 carbon atom.Mole number by the oxyalkylene of adduction such as ethylene oxide is about 1-50.Lipid acid comprises the straight or branched that contains 4-30 carbon atom, saturated or unsaturated fatty acids.
Comprise polyvinyl alcohol, polyoxyethylene glycol, ethylene oxide-propylene oxide copolymer, Natvosol, hydroxypropylcellulose, methylcellulose gum and starch derivative as the nonionic of stablizer (d) or two oligomers or superpolymer.
Anionic oligomer or superpolymer as stablizer (e) comprise:
(1) polymkeric substance can be water-soluble or water dispersible, this polymkeric substance contains one or more monomers that is selected from unsaturated carboxylic acid and derivative thereof,
(2) polymkeric substance can be water-soluble or water dispersible, this polymkeric substance contains the unsaturated sulfonic acid or derivatives thereof,
(3) the formalin condenses of sulfonated polynuclear aromatic compound, described aromatic substance can contain alkyl as substituting group,
(4) two or more (1) are to the mixture of the material of (3).
Above-mentioned polymkeric substance (1) can be made by one or more monomers that is selected from unsaturated and monocarboxylic acid (for example vinylformic acid, methacrylic acid), di-carboxylic acid (for example toxilic acid), its an alkali metal salt (for example sodium salt), its ammonium salt, its organic amine salt (for example triethanolamine salt).These monomers can use with the monomer of its copolymerization with other, for example, vinyl-acetic ester, iso-butylene, diisobutylene, vinylbenzene, alkyl acrylate, alkyl methacrylate, (methyl) Hydroxyethyl acrylate, (methyl) vinylformic acid polyoxyalkylene esters, (methyl) acrylamide and diacetone-acryloamide(DAA).
These monomers can carry out polymerization or copolymerization according to a conventional method.The not strict restriction of the polymerization degree of the ratio of monomer component and the polymkeric substance of wishing to get or multipolymer, but the polymkeric substance or the multipolymer that obtain must be water-soluble or water dispersible.
The example of polymkeric substance (1) comprising: acrylate copolymer, Sipacril 2739OF, vinylformic acid/Sipacril 2739OF, vinylformic acid/methacrylic acid polyoxyethylene enoate copolymer, vinylformic acid/methyl acrylate copolymer, acrylic acid multipolymer, vinylformic acid/maleic acid, toxilic acid/isobutylene copolymers, toxilic acid/styrol copolymer and basic metal, ammonia and organic amine salt.These polymkeric substance and multipolymer can use separately, and perhaps two or more use together.
The example of above-mentioned polymkeric substance (2) comprising: the unsaturated sulfonic acid polymerization and polymkeric substance, described unsaturated sulfonic acid is for example: styrene sulfonic acid, 2-acrylamide-2-methyl propane sulfonic acid, vinyl sulfonic acid, methylpropenyl sulfonic acid, propenyl sulfonic acid or the like, perhaps unsaturated sulfonic acid and other monomer such as hydrophobic monomer (alkyl acrylate for example, alkyl methacrylate, vinyl alkyl ethers, vinyl-acetic ester, ethene, propylene, butylene, divinyl, diisobutylene, vinylchlorid, 1,2-dichloroethene, vinyl cyanide and vinylbenzene), hydrophilic monomer (vinylformic acid for example, methacrylic acid, toxilic acid, fumaric acid, maleic anhydride, vinyl alcohol, acrylamide, Methacrylamide, diacetone-acryloamide(DAA), the N-vinyl pyrrolidone, 2-acrylamide-2-methyl propane sulfonic acid, methallyl sulfonic acid, xylene monosulfonic acid, and naphthene sulfonic acid) copolymerization and multipolymer.Wherein the polymkeric substance of styrene sulfonate and multipolymer are preferred.
The polymkeric substance of styrene sulfonate can make by polymerizing styrene sulfonate or sulfonated polystyrene.The styrene sulfonate polymkeric substance has the structure shown in the following formula:
The molecular weight of styrene sulfonate polymkeric substance is preferably 1000 or more, is more preferably 10,000-3,000,000.In the following formula, M represents basic metal (for example, lithium, sodium, potassium), ammonium, alkylamine or alkanolamine.
The multipolymer of styrene sulfonate can by styrene sulfonate and other monomer copolymerization makes or sulfonated phenylethylene and other monomeric multipolymer make.The preferred embodiment of multipolymer comprises: (methyl) vinylformic acid-styrene sulfonic acid multipolymer.In this multipolymer, the mol ratio of (methyl) acrylic acid groups and styrene sulfonic acid is 1/10-10/1 preferably, is more preferably 1/3-7/1.Molecular-weight average preferably 1,000-1,000,000, be more preferably 10,000-700,000.The example of copolymer salt comprises sodium salt, sylvite, ammonium salt, diethanolamine salt, triethanolamine salt, a Virahol amine salt, diisopropanol amine salt, tri-isopropanolamine salt and 2-amino-2-methyl propane-1,3-two alkoxide.In this example, non-neutralizable fraction can be stayed in the multipolymer, as long as they do not make the properties deterioration of multipolymer.
The compound that contains aromatic ring in anthracene, xylogen or the petroleum residues that above-mentioned condenses (3) can replace by benzene, the naphthalene of alkyl replacement, anthracene, the alkyl that naphthalene, alkyl are replaced carries out sulfonation reaction according to a conventional method, is carried out to reactant salt subsequently and makes with formaldehyde condensation.In this example, the polymerization degree is 2-30 preferably, is more preferably 3-10.When the polymerization degree less than 2 the time, condensation is insufficient, and when the polymerization degree greater than 30 the time, it is very high that the molecular weight of polymkeric substance becomes, this is disadvantageous, for example the solubility in water.
Various aromatic substance all can be used, and preferred example comprises: xylogen, dimethylbenzene, toluene, naphthalene and moieties contain the alkylnaphthalene of 1-6 carbon atom.These aromatic substance can be used separately, also can two or more use together.
The example of condenses (3) comprising: the formalin condenses of following substances: mahogany acid derivative, lignosulfonic acid acid salt derivative, naphthalenesulfonate derivative, xylene monosulfonic acid salt derivative and alkyl benzene sulphonate (ABS) salt derivative.The example of its salt comprises basic metal (for example sodium, potassium) salt, alkaline-earth metal (for example calcium) salt, amine salt, ammonium salt or the like.
The preferred embodiment of stablizer (e) comprises homopolymer or multipolymer, the homopolymer of 3-sulfo group propyl group (methyl) acrylate salt or homopolymer or multipolymer, iso-butylene or the diisobutylene copolymer-maleic anhydride of multipolymer, formalin-naphthalene sulfonic acid condensate, lignosulfonic acid, polycyclic aromatic sulfonic acid copolymer, vinylformic acid and maleic anhydride of the homopolymer of vinylbenzene-sulfonic acid copolymer, acrylamide tertiary butyl sulfonic acid or multipolymer, vinylsulfonate.
In stablizer (a)-(e), (a) and (b), (c) and (e) be preferred, (a) and (b) and (e) be preferred.
The solid content of latex is generally 5-60%(weight).The concentration that adds the stablizer of the present invention in the nature rubber latex of deproteinization is 0.01-10%(weight), 0.1-5%(weight preferably), based on the gross weight of latex.If the concentration of stablizer, then can not obtain satisfied stabilising effect less than 0.01%.And concentration is uneconomic above 10%.
The present invention will further describe with embodiment, but should know that the present invention is only limited to these embodiment.Except that specifying, all per-cent and ratios are all represented with weight.
Embodiment 1-2
Handle the high ammonia emulsion of natural rubber with proteolytic enzyme (proteolytic enzyme of alkali) and tensio-active agent (60: 40 mixtures of Sodium dodecylbenzene sulfonate and polyoxyethylene (9 moles) lauryl ether), make the nature rubber latex of deproteinization, this emulsion does not have 3280cm in infrared spectra
-1The polypeptide absorption peak at place.Concentration added shown in every kind of stablizer shown in the table 1 pressed, and regulated total solids level to 55 ± 0.2%, obtained the nature rubber latex of stable deproteinization.
The mechanical stability of the emulsion that obtains is estimated with following test method (JIS K 6381).For relatively, add concentration and be the emulsion that 0.005% Sodium Lauryl Sulphate BP/USP makes as stablizer and the test that uses the same method the emulsion (Comparative Examples) that does not contain stablizer.The results are shown in Table 1.
The mechanical stability test method:
Latex is put into sample pot, by rotating an axle vigorous stirring with fixing speed.(MST, second) expression is used from beginning to be stirred to appearance and significantly condensed the required time to mechanical stability.Usually MST is not less than 500 seconds latex and is considered to stable.
Table 1
Embodiment stabilizer concentration MST (second)
(weight %)
1 Sodium Lauryl Sulphate BP/USP (Emal 10 powder
* 1) 1.0 1200
2 potassium oleate (FR-14
* 2) 0.5 600
3 Sodium dodecylbenzene sulfonatees (Neopelex F-65
* 3) 0.5 1300
4 polyoxyethylenes (9) nonylplenyl ether 3.0 1100
(Emulgen 909
*4)
5 polyoxyethylenes (20) sorbitan oil base ester 5.0 1400
(Rheodor TWO-120
*5)
6 lauryl sodium phosphates 2.0 1000
The 7 six glyceraloleates (polymerization degree: 6) 2.5 900
8 polyoxyethylenes (10)-oleic acid ester 3.0 1200
(Emanon 4110
*6)
9 lauryl glucosides 1.0 700
The sodium salt 1.0 800 of 10 formalin-naphthalene sulfonic acid condensate
(Demol N
* 7) (condensation degree (n)=5)
11 lauryl ethanoyl trimethyl-glycines 2.0 1100
(Lauryl acetobetaine)(Amphitol 20BS
*8)
12 polyvinyl alcohol (saponification deg: 78.5-81.5 mole %) 2.5 1000
13 polyoxyethylenes (3) sodium lauryl tri(oxyethyl) sulfate 0.5 1800＜
14 polyoxyethylenes (20) nonylplenyl ether sodium sulfate 3.0 800
15 pairs of (2-ethylhexyl) sodium sulfo-succinates 2.0 600
16 sodium polyacrylates (Mw=about 8,000) 1.0 900
17 vinylformic acid/maleic acid 1.0 650
(Mw=about 4,000)
Comparative example Sodium Lauryl Sulphate BP/USP 0.005 210
Comparative Examples does not have-70
Annotate: (1)
*1 to
*8 all is the trade name of the product of Kao Corp.
(2) numeral in the parantheses is meant the mole number that adds olefin oxide, except the special instruction.
By the result of table 1 as seen, add the mechanical stability that stablizer of the present invention can improve the nature rubber latex of deproteinization greatly.
Can improve the mechanical stability of the nature rubber latex of deproteinization with checking stablizer of the present invention as mentioned above, can provide stay-in-grade emulsion like this and needn't worry allergy.
More than be detailed introduction of the present invention and specific embodiment, clearly, those of ordinary skills can make various modifications and without prejudice to spirit of the present invention, not exceed scope of the present invention.
Claims (2)
1, a kind of method of nature rubber latex of stable deproteinization comprises adding a kind of stablizer that is selected from following one group of material in the nature rubber latex of deproteinization:
(a) anion surfactant,
(b) amphoterics,
(c) nonionogenic tenside,
(d) nonionic or amphoteric oligopolymer or superpolymer and
(e) anionic oligomer or superpolymer,
The consumption of stability is 0.01-10% (weight), based on the gross weight of latex.
2, a kind of being selected from:
(a) anion surfactant,
(b) amphoterics,
(c) nonionogenic tenside,
(d) nonionic or amphoteric oligopolymer or superpolymer and
(e) anionic oligomer or superpolymer,
Compound as the purposes of the stablizer of the nature rubber latex of deproteinization.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP111765/93 | 1993-05-13 | ||
| JP111765/1993 | 1993-05-13 | ||
| JP11176593A JP3248978B2 (en) | 1993-05-13 | 1993-05-13 | Stabilizer for deproteinized natural rubber latex and method for producing stabilized deproteinized natural rubber latex using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1096301A true CN1096301A (en) | 1994-12-14 |
| CN1068603C CN1068603C (en) | 2001-07-18 |
Family
ID=14569621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94106006A Expired - Lifetime CN1068603C (en) | 1993-05-13 | 1994-05-13 | Means for stabilizing deproteinized natural rubber latex |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5610212A (en) |
| EP (1) | EP0630907B1 (en) |
| JP (1) | JP3248978B2 (en) |
| CN (1) | CN1068603C (en) |
| AU (1) | AU669617B2 (en) |
| DE (1) | DE69419839T2 (en) |
| ES (1) | ES2135506T3 (en) |
| TW (1) | TW321653B (en) |
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| KR102081764B1 (en) | 2016-09-01 | 2020-02-26 | 주식회사 엘지화학 | Latex composition for dip-forming and the product prepared thereby |
| WO2021133188A1 (en) * | 2019-12-25 | 2021-07-01 | Публичное Акционерное Общество "Сибур Холдинг" (Пао "Сибур Холдинг") | Composition for stabilizing latex and method for producing same |
| US11407883B2 (en) * | 2020-02-03 | 2022-08-09 | Illinois Tool Works Inc. | High performing low viscosity tire sealant |
| CN113651902B (en) * | 2021-08-24 | 2023-06-13 | 中国热带农业科学院橡胶研究所 | Preparation method of deproteinized natural latex |
| CN115057956B (en) * | 2022-06-28 | 2024-06-25 | 万华化学集团股份有限公司 | High-solid-content narrow-distribution polybutadiene latex agglomeration method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE519483C (en) * | 1926-11-11 | 1931-02-28 | I G Farbenindustrie Akt Ges | Process for preserving and processing rubber milk |
| GB1366934A (en) * | 1971-08-10 | 1974-09-18 | Malaysia Rubber Res Inst | Treatment of rubber |
| GB2011933B (en) * | 1978-01-10 | 1982-05-19 | Malaysia Rubber Res Inst | Preservation of latex |
| GB2098222B (en) * | 1981-05-07 | 1984-08-15 | Malaysia Rubber Res Inst | Processing of hevea latex |
| US4455265A (en) * | 1982-03-03 | 1984-06-19 | The Firestone Tire & Rubber Company | Stabilizer for low ammonia natural rubber latex compounds |
| JPS62101601A (en) * | 1985-10-29 | 1987-05-12 | Toyo Soda Mfg Co Ltd | Production of powdered rubber |
-
1993
- 1993-05-13 JP JP11176593A patent/JP3248978B2/en not_active Expired - Lifetime
-
1994
- 1994-05-10 DE DE69419839T patent/DE69419839T2/en not_active Expired - Lifetime
- 1994-05-10 EP EP94107282A patent/EP0630907B1/en not_active Expired - Lifetime
- 1994-05-10 ES ES94107282T patent/ES2135506T3/en not_active Expired - Lifetime
- 1994-05-12 TW TW083104283A patent/TW321653B/zh not_active IP Right Cessation
- 1994-05-12 AU AU63069/94A patent/AU669617B2/en not_active Expired
- 1994-05-13 US US08/241,989 patent/US5610212A/en not_active Expired - Lifetime
- 1994-05-13 CN CN94106006A patent/CN1068603C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102893148A (en) * | 2011-05-19 | 2013-01-23 | 马来西亚橡胶局 | Method of quantitative measurement of mechanical stability time (mst) of latex suspensions and the apparatus for use in the method |
| CN102893148B (en) * | 2011-05-19 | 2015-11-25 | 马来西亚橡胶局 | For method and the equipment that uses in the process of quantitative measurment latex suspended matter mechanical stability time (MST) |
| CN107236060A (en) * | 2017-07-19 | 2017-10-10 | 海南职业技术学院 | Rubber is gathered and guarantor property method |
| CN111205379A (en) * | 2020-03-18 | 2020-05-29 | 田晓慧 | Method for processing natural latex by creaming |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1068603C (en) | 2001-07-18 |
| US5610212A (en) | 1997-03-11 |
| AU6306994A (en) | 1994-11-17 |
| JP3248978B2 (en) | 2002-01-21 |
| DE69419839T2 (en) | 1999-12-16 |
| EP0630907A1 (en) | 1994-12-28 |
| JPH06322003A (en) | 1994-11-22 |
| ES2135506T3 (en) | 1999-11-01 |
| TW321653B (en) | 1997-12-01 |
| AU669617B2 (en) | 1996-06-13 |
| DE69419839D1 (en) | 1999-09-09 |
| EP0630907B1 (en) | 1999-08-04 |
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